CN106575700B - 铁电体陶瓷及其制造方法 - Google Patents
铁电体陶瓷及其制造方法 Download PDFInfo
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- CN106575700B CN106575700B CN201580038020.0A CN201580038020A CN106575700B CN 106575700 B CN106575700 B CN 106575700B CN 201580038020 A CN201580038020 A CN 201580038020A CN 106575700 B CN106575700 B CN 106575700B
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Abstract
以提高压电特性为课题。本发明的一个方式是铁电体陶瓷,其特征在于,具备Pb(Zr1‑ATiA)O3膜和形成在所述Pb(Zr1‑ATiA)O3膜上的Pb(Zr1‑ xTix)O3膜,所述A以及所述x满足下述式1~式3。0≤A≤0.1…式1;0.1<x<1…式2;A<x…式3。
Description
技术领域
本发明涉及铁电体陶瓷及其制造方法。
背景技术
对现有的Pb(Zr,Ti)O3(以下称作“PZT”)钙钛矿型铁电体陶瓷的制造方法进行说明。
在4英寸Si晶片上形成膜厚300nm的SiO2膜,在该SiO2膜上形成膜厚5nm的TiOX膜。接下来,在该TiOX膜上形成例如取向于(111)的膜厚150nm的Pt膜,在该Pt膜上用旋涂机旋转涂敷PZT溶胶凝胶溶液。这时的旋转条件是以1500rpm的旋转速度旋转30秒钟、以4000rpm的旋转速度旋转10秒钟的条件。
接下来,将该涂敷后的PZT溶胶凝胶溶液在250℃的热板上加热保持30秒钟来使其干燥,在除去水分后,进一步在保持于500℃的高温的热板上加热保持60秒钟,来进行预烧制。将这一过程重复多次来生成膜厚150nm的PZT无定形膜。
接下来,对PZT无定形膜使用加压式灯退火装置(RTA:rapidly thermal anneal)进行700℃的退火处理,来进行PZT结晶化。如此结晶化后的PZT膜由钙钛矿结构构成(例如参考专利文献1)。
现有技术文献
专利文献
专利文献1:WO2006/087777
发明内容
发明要解决的课题
本发明的一个方式以提高压电特性作为课题。
用于解决课题的手段
以下说明本发明的各种方式。
[1]铁电体陶瓷的特征在于,具备:Pb(Zr1-ATiA)O3膜;和形成在所述Pb(Zr1-ATiA)O3膜上的Pb(Zr1-xTix)O3膜,所述A以及所述x满足下述式1~式3。
0≤A≤0.1…式1
0.1<x<1…式2
A<x…式3
另外,Pb(Zr1-xTix)O3膜取向于(001)。
[2]在上述[1]的基础上,铁电体陶瓷的特征在于,所述A是0,所述Pb(Zr1-ATiA)O3是PbZrO3膜。
另外,Pb(Zr1-xTix)O3膜取向于(001)。
[3]在上述[1]或[2]的基础上,铁电体陶瓷的特征在于,所述Pb(Zr1-ATiA)O3膜形成在氧化膜上。
另外,所述氧化膜优选是钙钛矿结构的氧化物。
[4]在上述[3]的基础上,铁电体陶瓷的特征在于,所述氧化膜是Sr(Ti,Ru)O3膜。
另外,所述Sr(Ti,Ru)O3膜优选是Sr(Ti1-xRux)O3膜,所述x满足下述式4。
0.01≤x≤0.4…式4
[5]在上述[1]至[4]中任一项的基础上,铁电体陶瓷的特征在于,所述Pb(Zr1- ATiA)O3膜形成在电极膜上。
[6]在上述[5]的基础上,铁电体陶瓷的特征在于,所述电极膜由氧化物或金属构成。
另外,所述氧化物可以是Sr(Ti1-xRux)O3膜,所述x满足下述式4。
0.01≤x≤0.4…式4
[7]在上述[5]或[6]的基础上,铁电体陶瓷的特征在于,所述电极膜是Pt膜或Ir膜。
另外,Pt膜取向于(100)。
[8]在上述[5]至[7]中任一项的基础上,铁电体陶瓷的特征在于,所述电极膜形成在ZrO2膜上。
另外,ZrO2膜取向于(100)。
[9]在上述[5]至[8]中任一项的基础上,铁电体陶瓷的特征在于,所述电极膜形成在Si基板上。
另外,Si基板取向于(100)。
[10]铁电体陶瓷的制造方法是在Pb(Zr1-ATiA)O3膜上形成Pb(Zr1-xTix)O3膜的铁电体陶瓷的制造方法,该铁电体陶瓷的制造方法的特征在于,所述A以及所述x满足下述式1~式3。
0≤A≤0.1…式1
0.1<x<1…式2
A<x…式3
另外,Pb(Zr1-xTix)O3膜取向于(001)。
[11]在上述[10]的基础上,铁电体陶瓷的制造方法的特征在于,所述A是0,所述Pb(Zr1-ATiA)O3膜是PbZrO3膜。
另外,Pb(Zr1-xTix)O3膜取向于(001)。
[12]在上述[10]或[11]的基础上,铁电体陶瓷的制造方法的特征在于,将Pb(Zr1- ATiA)O3的前体溶液涂敷在基板上,在5atm以上(优选7.5气压以上)的氧气氛中进行结晶化,由此形成所述Pb(Zr1-ATiA)O3膜。
另外,在上述的本发明的各种方式中,当说在特定的B(以下称作“B”)上(或下)形成特定的C(以下称作“C”)(形成C)时,并不限定于在B上(或下)直接形成C(形成C)的情况,还包括在不妨碍本发明的一个方式的作用效果的范围内在B上(或下)隔着其他构成来形成C(形成C)的情况。
发明的效果
通过应用本发明的一个方式,能提高压电特性。
附图说明
图1是说明本发明的一个方式所涉及的铁电体陶瓷的制造方法的示意性剖面图。
图2是说明本发明的一个方式所涉及的铁电体陶瓷的制造方法的示意性剖面图。
图3(A)~(C)是用于说明基于实施例1的样本的制造方法的剖面图。
图4是基于实施例1的成膜至图3(A)所示的Pt膜13为止的样本的XRD(X-RayDiffraction)曲线图。
图5是表示图3(A)所示的样本的XRD衍射结果的曲线图。
图6是表示图3(C)所示的样本的XRD衍射结果的曲线图。
图7是表示作为(400)取向和(004)取向相混合的比较例的PZT膜的样本的XRD衍射结果的曲线图。
图8是用于说明基于实施例2的样本的制造方法的剖面图。
图9是用于说明基于比较例的样本的制造方法的剖面图。
图10是样本4(实施例)的XRD曲线图。
图11是样本6(实施例)的XRD曲线图。
图12是样本9(比较例)的XRD曲线图。
图13是样本1(实施例)的XRD曲线图。
图14是样本2(实施例)的XRD曲线图。
图15是样本3(实施例)的XRD曲线图。
图16是样本4(实施例)的XRD曲线图。
图17是样本5(实施例)的XRD曲线图。
图18是样本6(实施例)的XRD曲线图。
图19是用于说明半峰全宽(FWHM)的图。
图20是样本7(比较例)的XRD曲线图。
图21是样本8(比较例)的XRD曲线图。
图22是样本9(比较例)的XRD曲线图。
图23是表示PZO的结晶结构为斜方晶的图。
图24(A)是实施例3的PZT膜的XRD图谱,(B)是实施例3的PZO膜的XRD图谱。
具体实施方式
以下使用附图来详细说明本发明的实施方式以及实施例。但本发明并不限定于以下的说明,能不脱离本发明的趣旨以及其范围地对其形态以及详细进行各种变更,只要是本领域技术人员都能容易理解这一点。因此,本发明并不限定解释为以下所示的实施方式的记载内容以及实施例。
[第1实施方式]
图1是说明本发明的一个方式所涉及的铁电体陶瓷的制造方法的示意性剖面图。
准备基板(未图示)。作为该基板,能使用各种基板,例如能使用Si单晶或蓝宝石单晶等的单晶基板、在表面形成金属氧化物膜的单晶基板、在表面形成多晶硅膜或硅化物膜的基板等。另外,在本实施方式中使用取向于(100)的Si基板。
接下来,在Si基板(未图示)上以550℃以下的温度(优选500℃的温度)通过蒸镀法形成ZrO2膜(未图示)。该ZrO2膜取向于(100)。另外,若以750℃以上的温度通过蒸镀法形成ZrO2膜,则该ZrO2膜不取向于(100)。
在本说明书中,取向于(100)、取向于(200)和取向于(400)实质上相同,另外,取向于(001)、取向于(002)和取向于(004)实质上相同。
之后在ZrO2膜上形成下部电极103。下部电极103由金属或氧化物所构成的电极膜形成。作为金属所构成的电极膜,例如使用Pt膜或Ir膜。作为氧化物所构成的电极膜,例如是Sr(Ti1-xRux)O3膜,x满足下述式4。
0.01≤x≤0.4…式4
在本实施方式中,在ZrO2膜上以550℃以下的温度(优选400℃的温度)通过溅射(sputtering)形成基于外延生长的Pt膜103来作为下部电极。该Pt膜103取向于(200)。
接下来,在下部电极103上形成PbZrO3膜(以下也称作“PZO膜”)104。该PZO膜104能用各种方法形成,例如能用溶胶凝胶法、CVD法、溅射法形成。在用溶胶凝胶法形成PZO膜104的情况下,将PZO的前体溶液涂敷在基板上,在5atm以上(优选7.5气压以上)的氧气氛中进行结晶化即可。另外,PZO的晶格常数分别为a=8.232埃、b=11.776埃、c=5.882埃。a轴长度成为平均的钙钛矿(埃)的约2倍,c轴长度成为 b轴长度成为关于该PZO的晶格常数的变化,基本上是钙钛矿八面体结晶的旋转,在其中加进八面体的形变,b轴方向的周期成为2倍。
PZO如图23所示那样是斜方晶。因此,PZO看上去晶格常数变大。这是因为,钙钛矿纵旋转45°程度,正好将旋转后的结晶如虚线部分那样包围周围地像大的结晶那样对待。即,以看上去a、b、c轴的长度变得非常长的方式来对待是斜方晶的惯例。实际的PZO是实线那样的结晶,是通常的钙钛矿结晶。
接下来,在PZO膜104上形成PZT膜105。该PZT膜105是Pb(Zr1-xTix)O3膜,x满足下述式2。Pb(Zr1-xTix)O3膜取向于(001)。
0<x<1…式2’
另外,在本说明书中,“PZT膜”也包括在Pb(Zr,Ti)O3中含有杂质的构成,即使含有该杂质,只要不使PZT膜的压电体的功能消失,就可以含有各种杂质。
以下详细说明PZT膜的形成方法的一例。
作为PZT膜形成用溶胶凝胶溶液,使用以丁醇为溶媒的添加了不足70%~90%的量的铅的、浓度10重量%浓度的E1溶液。
在该溶胶凝胶溶液中将二甲基氨基乙醇这样的具有氨基的碱性乙醇按照体积比以E1溶胶凝胶溶液∶二甲基氨基乙醇=7∶3的比例添加,示出强到pH=12的强碱性。
使用上述本溶液来进行PZT无定形膜的旋涂形成。旋涂机使用“ミカサ株式会社”制MS-A200进行。首先,在以800rpm旋转5秒、以1500rpm旋转10秒后,逐渐以10秒使旋转上升到3000rpm,之后在150℃的热板(“アズワン株式会社”制陶瓷热板AHS-300)上在大气中放置5min,之后在300℃的热板(同AHS-300)上在相同的大气中放置10min,之后冷却到室温。通过将这一过程重复5次,从而在PZO膜104上形成所期望的膜厚200nm的PZT无定形膜。将其制作多片。
接下来,通过在加压氧气氛中对上述的PZT无定形膜进行热处理,从而在PZO膜104上形成使PZT无定形膜结晶化后的PZT膜105。另外,PZT的晶格常数的一例是0.401nm。
也可以在如上述那样形成了PZT膜105后对PZT膜105进行修整(polling:ポ一リング)处理。
另外,在本实施方式中,用溶胶凝胶法形成PZT膜105,但也可以用溅射法形成PZT膜。
根据本实施方式,通过将PZO膜104用作PZT膜105的初始核层(即缓冲层),能提高PZT膜105的压电特性。详细来说明,PbZrO3(PZO)是Pb(Zr1-xTix)O3(PZT)的相图中Ti比率0(零)的情况,是反铁电体,但由于在Pb(Zr1-xTix)O3之中c轴长最长,所以PZO在将全部PZT的c轴长拉长的方向上起作用,能容易得到该结构所能取得的最大的压电性能。即,通过使PZO作为初始核,PZT整体在PZO初始核的晶轴受到影响,在PZT膜整体中c晶轴变得易于拉长,即变得易于极化,能容易地取出压电性。
另外,在本实施方式中,在下部电极103上形成Pb(Zr,Ti)O3的相图中Ti比率0的PZO膜104,在PZO膜104上形成Pb(Zr1-xTix)O3膜105(0<x<1…式2’),但也可以在非常小的Ti比率的Pb(Zr1-ATiA)O3膜上形成Pb(Zr1-xTix)O3膜。其中,A以及x满足下述式1~式3。Pb(Zr1-xTix)O3膜取向于(001)。
0≤A≤0.1…式1
0.1<x<1…式2
A<x…式3
通过满足上述式1,即,通过使Ti比率为10%以下,用作初始核的Pb(Zr1-ATiA)O3膜就成为反铁电性斜方晶相的PZT(即Pb(Zr,Ti)O3的相图中斜方晶区域(ortho区域)的PZT),Pb(Zr1-ATiA)O3在将全部Pb(Zr1-xTix)O3(PZT)的c轴长拉长的方向上起作用,能得到与上述实施方式相同的效果。
[第2实施方式]
图2是说明本发明的一个方式所涉及的铁电体陶瓷的制造方法的示意性剖面图,对与图1相同部分标注同一标号。
由于直至Si基板(未图示)、ZrO2膜(未图示)以及下部电极103为止用与第1实施方式相同的方法来形成,因此省略说明。
接下来,在下部电极103上形成氧化膜106。该氧化膜106是钙钛矿结构的氧化物即可,例如是Sr(Ti,Ru)O3膜。该Sr(Ti,Ru)O3膜是Sr(Ti1-xRux)O3膜,x满足下述式4,通过溅射来形成。这时的溅射靶使用Sr(Ti1-xRux)O3的烧结体。其中,x满足下述式4。
0.01≤x≤0.4(优选0.05≤x≤0.2)…式4
另外,Sr(Ti1-xRux)O3膜的x为0.4以下是因为,若使x超过0.4,则Sr(Ti1-xRux)O3膜成为粉,无法充分凝固。
之后,在加压氧气氛中通过RTA(Rapid Thermal Anneal:快速热退火)使Sr(Ti1- xRux)O3膜结晶化。Sr(Ti1-xRux)O3膜是锶、钛和钌的复合氧化物,是取钙钛矿结构的化合物。
接下来,用与第1实施方式相同的方法在氧化膜106上形成PZO膜104。接下来,在PZO膜104上用与第1实施方式相同的方法形成PZT膜105。PZT膜105取向于(001)。
在本实施方式中也能得到与第1实施方式相同的效果。
另外,在本实施方式中,在氧化膜106上形成PZO膜104,在PZO膜104上形成PZT105,但也可以在非常小的Ti比率的Pb(Zr1-ATiA)O3膜上形成Pb(Zr1-xTix)O3膜。其中,A以及x满足下述式1~式3。Pb(Zr1-xTix)O3膜取向于(001)。
0≤A≤0.1…式1
0.1<x<1…式2
A<x…式3
通过满足上述式1而能得到与第1实施方式相同的效果。
另外,也可以将上述的第1以及第2实施方式适当组合来实施。
[实施例1]
图3(A)~(C)是用于说明基于实施例1的样本的制造方法的剖面图。
如图3(A)所示那样,在具有(100)的结晶面的6英寸的Si基板11上通过反应性蒸镀法对ZrO2膜12进行成膜。这时的蒸镀条件如表1所示。该ZrO2膜12取向于(100)。
接下来,在ZrO2膜12上通过溅射对膜厚100nm的Pt膜13进行成膜。这时的成膜条件如表1所示。该Pt膜13取向于(200)。图4示出这时的XRD图谱。
[表1]
实施例
工艺 | 蒸镀 | DC-溅射 |
Depo Vac | 6.90E-03 | 3.20E-02 |
Depo源 | Zr+O<sub>2</sub> | Pt |
ACC/发射 | 7.5kV/1.50mA | DC/100W |
总厚度(nm) | 13.4 | 100 |
Depo时间(sec) | 930 | 720 |
SV deg(Tsub) | 500℃ | 400℃ |
MFC O<sub>2</sub> | 5sccm | Ar:16sccm |
图4表示成膜至图3(A)所示的Pt膜13为止的样本的XRD衍射结果。从该XRD曲线图确认到,Pt膜取向于(400),2Θ=103.71°。另外,在图4中,纵轴是强度,横轴是2Θ。
接下来,在Pt膜13上形成将PbZrO3膜(以下称作“PZO膜”)和Pb(Zr0.55Ti0.45)O3膜(以下称作“PZT膜”)依次层叠而成的层叠膜15。详细地,在Pt膜13上用溶胶凝胶法涂敷膜厚250nm的PZO膜。这时的条件如以下。
将1.4mol/kg浓度的1.3PbZrO3形成用MOD溶液(“豊島製作所”制Lot.00050667-1)、乙醇、2-丁氧基乙醇调配在一起成为1000ml(分别以1∶1∶1的比例混合),在其中添加20g的聚乙烯吡咯烷酮(日本触媒K-30)这样的白色粉末,将以搅拌溶解后的溶液作为PZO250nm的原料溶液的、该溶液3ml滴下到6in晶片上,在以3000rpm进行10sec旋转涂敷后,在150℃热板上保持30sec,接下来在250℃热板上保持90sec,之后在1atm-O2气氛中以600℃烧结3min。
接下来,在PZO膜上用溅射法形成膜厚2500nm的PZT膜。这时的溅射条件与实施例2相同。图5示出这时的XRD图谱。
图5是表示图3(A)所示的样本的XRD衍射结果的曲线图。从该XRD曲线图确认到,层叠膜15的PZT膜取向于(004),2Θ=97.1°。另外,在图5中,纵轴是强度,横轴是2Θ。
接下来,如图3(B)所示,在对Si基板11全部进行研磨,并用ICP(InductiveCoupling Plasma:感应耦合等离子)蚀刻机除去ZrO2膜12后,如图3(C)所示,通过铣削将Pt膜13除去。由此,仅留下PZT/PZO的层叠膜15。图6示出这时的XRD图谱。
图6是表示图3(C)所示的样本的XRD衍射结果的曲线图。根据该XRD曲线图,层叠膜15的PZT膜在2Θ=96.97°得到仅(004)的峰值。由此,可知PZT/PZO的层叠膜15是(001)c轴单一取向膜。另外,在图6中,纵轴是强度,横轴是2Θ。
在此,PZT(400)存在于与Pt(400)相同的位置,在PZT膜是(400)取向和(004)取向的混合膜的情况下,图7所示的PZT(004)的峰值强度与图6所示的PZT(004)单一膜相比而更易于变弱。此外,图7所示的PZT大多是2Θ≥98°。另外,图7是表示作为(400)取向和(004)取向相混合的比较例的PZT膜的样本的XRD衍射结果的曲线图。
当然,在PZT(400)和(004)的混合膜的情况下,即使设为图3(C)所示那样的仅PZT的膜结构,也存在图7所示的PZT(400)的峰值。因此,根据图6所示的XRD曲线图,图3(C)所示的PZT膜可以说是(001)c轴单一取向膜。
根据本实施例,通过将PZO膜用作PZT膜的初始核层(即缓冲层),从而能得到单一取向于(001)的c轴的PZT膜,能提高PZT膜的压电特性。详细来说明,PbZrO3(PZO)是Pb(ZrxTi1-x)O3(PZT)的相图中Ti比率0(零)的情况,由于在Pb(ZrxTi1-x)O3之中c轴长最长,因此PZO在将全部PZT的c轴长拉长的方向上起作用,由此易于极化,其结果是能容易地取出压电性。
[实施例2]
图8是用于说明基于实施例2的样本的制造方法的剖面图。
图8所示的样本的Si基板11、ZrO2膜12以及Pt膜13用与图3(A)所示的基于实施例1的样本相同的方法来制作。
接下来,在Pt膜13上通过溅射形成Sr(Ti0.8Ru0.2)O3膜(以下称作“STRO膜”)14。这时的溅射的条件如以下。
[STRO膜14的溅射条件]
工艺:RF-溅射
靶:Sr(Ti0.8Ru0.2)O3
RF功率:400W/13.56MHz
工艺压力:4Pa
气体流量Ar/O2(sccm):30/10
基板温度:600℃
工艺时间:20sec
膜厚:50nm
之后,通过RTA在加压氧气氛中使STRO膜14结晶化。这时的RTA的条件如以下。
[RTA的条件]
退火温度:600℃
导入气体:氧气体
压力:9kg/cm2
升温速率:100℃/sec
退火时间:5分钟
接下来,在STRO膜14上通过旋涂法对膜厚50~400nm的PZO膜16进行成膜。这时的成膜条件如以下的(1)~(3)。
(1)将1.4mol/kg浓度的1.3PbZrO3形成用MOD溶液(“豊島製作所”制Lot.00050667-1)、乙醇、2-丁氧基乙醇调配在一起成为1000ml(分别以1∶1∶1的比例混合),在其中添加10g聚乙烯吡咯烷酮(日本触媒K-30)这样的白色粉末,将以搅拌溶解后的溶液作为PZO-50nm的原料溶液的、该溶液3ml滴下到6in晶片上,在以5000rpm进行10sec旋转涂敷后,在150℃热板上保持30sec,接下来在250℃热板上保持90sec,之后在1atm-O2气氛中以600℃烧结3min,形成厚度50nm的PZO膜。
(2)将1.4mol/kg浓度的1.3PbZrO3形成用MOD溶液(“豊島製作所”制Lot.00050667-1)、乙醇、2-丁氧基乙醇调配在一起成为1000ml(分别以1∶1∶1的比例混合),在其中添加20g聚乙烯吡咯烷酮(日本触媒K-30)这样的白色粉末,将以搅拌溶解后的溶液作为PZO-250nm的原料溶液的、该溶液3ml滴下到6in晶片上,在以3000rpm进行10sec旋转涂敷后,在150℃热板上保持30sec,接下来在250℃热板上保持90sec,之后在1atm-O2气氛中以600℃烧结3min,形成厚度250nm的PZO膜。
(3)将1.4mol/kg浓度的1.3PbZrO3形成用MOD溶液(“豊島製作所”制Lot.00050667-1)、乙醇、2-丁氧基乙醇调配在一起成为1000ml(分别以1∶1∶1的比例混合),在其中添加20g聚乙烯吡咯烷酮(日本触媒K-30)这样的白色粉末,将以搅拌溶解后的溶液作为PZO-400nm的原料溶液的、该溶液3ml滴下到6in晶片上,在以1000rpm进行10sec旋转涂敷后,在150℃热板上保持30sec,接下来在250℃热板上保持90sec,之后在1atm-O2气氛中以600℃烧结3min,形成厚度400nm的PZO膜。
接下来,在PZO膜16上用溅射法形成膜厚1000~4000nm的Pb(Zr0.55Ti0.45)O3膜(以下称作“PZT膜”)17。这时的溅射条件如以下。
[溅射条件]
装置:RF磁控溅射装置
功率:1500W
气体:Ar/O2
压力:0.14Pa
温度:600℃
成膜速度:0.63nm/秒
成膜时间:1.3分钟
图9是用于说明基于比较例的样本的制造方法的剖面图,对与图8相同的部分标注同一标号。
图9所示的样本从图8所示的样本中去掉了PZO膜16,除PZO膜16以外是与图8所示的样本相同的膜结构,各膜的形成方法也相同。
[表2]
XRD衍射数据比较
表2所示的样本1~6是基于实施例2的样本,具有图8所示的膜结构。表2所示的样本7~9是基于比较例的样本,具有图9所示的膜结构。样本1~6各自的PZO膜16的膜厚以及样本1~9各自的PZT膜17的膜厚如以下。
取得样本1~9的XRD数据,将由该XRD数据取出的详细的数据在表2中示出。
图10是样本4(实施例)的XRD曲线图,图11是样本6(实施例)的XRD曲线图,图12是样本9(比较例)的XRD曲线图。图10~图12分别示出15°≤2Θ≤50°的范围。
如图10~图12所示,样本4、6、9的任一者,在2Θ≤50°的范围内,在结晶性上几乎都看不到差异,都是良好的PZT结晶膜。
图13是样本1(实施例)的XRD曲线图,图14是样本2(实施例)的XRD曲线图,图15是样本3(实施例)的XRD曲线图。图13~图15分别表示90°≤2Θ≤110°的范围。
图16是样本4(实施例)的XRD曲线图,图17是样本5(实施例)的XRD曲线图,图18是样本6(实施例)的XRD曲线图。图16~图18分别表示90°≤2Θ≤110°的范围。
图20是样本7(比较例)的XRD曲线图,图21是样本8(比较例)的XRD曲线图,图22是样本9(比较例)的XRD曲线图。图20~图22分别表示90°≤2Θ≤110°的范围。
在样本1~3(实施例)中,在作为初始核的PZO膜16为50~400nm的全部情况下,如图13~图15所示,(004)峰值存在于低到2Θ≤97°的非常低的低角度域。此外,即使是在作为初始核的PZO膜16的上部以膜厚1000~4000nm形成了PZT(55/45)膜17的情况下的样本4~6(实施例),也如图16~图18所示,(004)峰值存在于低到2Θ≤97°的非常低的低角度域。另外,如表2所示,在样本4~6(实施例)中,是PZT(004)峰值强度每膜厚1000nm为175000cps以上这样非常良好的结晶性良好。另外,如表2所示,在样本4~6(实施例)中,PZT(004)/Pt(400)峰值强度比率是(004)/(400)>60%。另外,如表2所示,在样本4~6(实施例)中,|(400)-(004)|的ac轴长的2Θ差非常大,大到|(400)-(004)|>6.5°,足够预测到剩余极化值大这一情况。
另外,如表2所示,在样本4~6(实施例)中,对于半峰全宽FWHM、所谓的半宽度(半価幅)来说,若FWHM<0.8°,则具有与单晶的半峰全宽同等的数值。另外,半峰全宽(fullwidth at half maximum,FWHM)是指图19所示的宽度(来自***-半宽(半值幅))。
另外,若将样本4~6(实施例)与用图9所示的制造方法制作的比较例的样本7~9(参考图20~图22)进行比较,则可知样本4~6(实施例)的PZT膜是优异的结晶膜。
根据本实施例,通过将PZO膜用作PZT膜的初始核层(即缓冲层),能得到单一取向于(001)的c轴的PZT膜,能提高PZT膜的压电特性。
[实施例3]
Si基板、ZrO2膜以及Pt膜用与基于实施例1的样本相同的方法制作。然后,用旋涂法在5000rpm-10sec的旋转条件下将PZO前体溶液(与实施例1、2相同的溶液)在Pt膜上涂敷厚度40nm的PZO。之后,按升温速度为10℃/sec、烧结环境为O2、10atm在烧结温度650℃下进行1min的结晶化。之后,进行XRD衍射评价,得到如图24(B)那样(001)取向的厚度40nm的PZO膜。
接下来,在该厚度40nm的PZO膜上直接继续用溅射法形成厚度4μm的PZT膜。这时的XRD图谱如图24(A)那样,能得到具有与(001)取向的PZO膜的晶格常数同等的晶格常数的、即保持PZO的c轴长不变的、厚度4μn的PZT(Zr/Ti=55/45:XRF分析值)膜。
对于在图24(B)的厚度40nm的PZO膜的情况下能明确确认到存在的ZrO2来说,若涂敷图24(A)的厚度4μm的PZT膜,使PZT膜的膜厚也成为4μm,则PZT强度变得相当强,虽然是同一基板,但在该XRD评价条件的情况下,也已经不能确认到ZrO2的存在。
标号的说明
11 Si基板
12 ZrO2膜
13 Pt膜
14 Sr(Ti0.8Ru0.2)O3膜(STRO膜)
15 依次层叠PbZrO3膜(PZO膜)和Pb(Zr0.55Ti0.45)O3膜(PZT膜)而成的层叠膜
16 PZO膜
17 Pb(Zr0.55Ti0.45)O3膜(PZT膜)
103 下部电极
104 PbZrO3膜(PZO膜)
105 PZT膜
106 氧化膜
Claims (11)
1.一种铁电体陶瓷,其特征在于,具备:
Sr(Ti1-yRuy)O3膜;
形成在所述Sr(Ti1-yRuy)O3膜上的、(001)取向的Pb(Zr1-ATiA)O3膜;和
形成在所述Pb(Zr1-ATiA)O3膜上的、(001)取向的Pb(Zr1-xTix)O3膜,
所述A、所述x以及所述y满足下述式1~式4,
0≤A≤0.1…式1
0.1<x<1…式2
A<x…式3
0.01≤y≤0.4…式4。
2.根据权利要求1所述的铁电体陶瓷,其特征在于,
所述A是0,
所述Pb(Zr1-ATiA)O3是PbZrO3膜。
3.根据权利要求1所述的铁电体陶瓷,其特征在于,
所述Sr(Ti1-yRuy)O3膜形成在电极膜上。
4.根据权利要求3所述的铁电体陶瓷,其特征在于,
所述电极膜是Pt膜或Ir膜。
5.根据权利要求3所述的铁电体陶瓷,其特征在于,
所述电极膜形成在ZrO2膜上。
6.根据权利要求5所述的铁电体陶瓷,其特征在于
所述ZrO2膜形成在Si基板上。
7.根据权利要求1所述的铁电体陶瓷,其特征在于,
所述Pb(Zr1-ATiA)O3膜是所述Pb(Zr1-xTix)O3膜的膜厚的1/10以下。
8.一种铁电体陶瓷的制造方法,包括:
通过溅射法在基板上形成Sr(Ti1-yRuy)O3膜的步骤;
在加压氧气氛中通过加热退火将所述Sr(Til-yRuy)O3膜结晶化的步骤;
在所述Sr(Ti1-yRuy)O3膜上通过溅射法或溶胶凝胶法形成(001)取向的Pb(Zr1-ATiA)O3膜的步骤;
在所述Pb(Zr1-ATiA)O3膜上通过溅射法或溶胶凝胶法形成(001)取向的Pb(Zr1-xTix)O3膜的步骤,
该铁电体陶瓷的制造方法的特征在于,
所述A、所述x以及所述y满足下述式1~式4,
0≤A≤0.1…式1
0.1<x<1…式2
A<x…式3
0.01≤y≤0.4…式4。
9.根据权利要求8所述的铁电体陶瓷的制造方法,其特征在于,
所述A是0,
所述Pb(Zr1-ATiA)O3膜是PbZrO3膜。
10.根据权利要求8所述的铁电体陶瓷的制造方法,其特征在于,
将包含Pb(Zr,Ti)O3的前体溶液涂敷在所述基板上,在5atm以上的氧气氛中进行结晶化,由此形成所述Pb(Zr1-ATiA)O3膜或所述Pb(Zr1-xTix)O3膜。
11.根据权利要求8所述的铁电体陶瓷的制造方法,其特征在于,
所述Pb(Zr1-ATiA)O3膜是所述Pb(Zrl-xTix)O3膜的膜厚的1/10以下。
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Fatigue Behaviour of Pb(Zr,Ti)O3/PbZrO3 multilayer Ferroelectric Thin films;Sedat ALKOY 等;《Japanese Journal of Applied Physics》;20060922;第36卷;第7275-7278页 * |
Sedat ALKOY 等.Fatigue Behaviour of Pb(Zr,Ti)O3/PbZrO3 multilayer Ferroelectric Thin films.《Japanese Journal of Applied Physics》.2006,第36卷 * |
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JP6598032B2 (ja) | 2019-10-30 |
CN106575700A (zh) | 2017-04-19 |
US20170158571A1 (en) | 2017-06-08 |
JPWO2016009698A1 (ja) | 2017-04-27 |
WO2016009698A1 (ja) | 2016-01-21 |
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